JP2016185152A - Lycopene composition having improved colorant property - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a crystalline lycopene composition having more satisfactory long-term stability and colorant property.SOLUTION: The invention targets to a tomato-derived composition containing lycopene with high concentration and an insoluble substrate with low (10% (w/w) or less) concentration. An unexpected characteristic of the composition is that lycopene crystal contained in the same can be pulverized to a size of less than 1 micron. A further advantage of the composition is improvement of its color characteristic. Therefore the invention also targets to use of the composition as a colorant for food, beverage, nutritional supplement products, or cosmetics.SELECTED DRAWING: None

Description

  The present invention is a composition comprising a high concentration of lycopene crystals and a low concentration of insoluble material, wherein the crystals have improved properties for use as colorants when compared to prior art preparations. , Relating to the composition.

  Prior art publication US 5,965,183 discloses and teaches a process for the preparation of stable lycopene concentrates. This method has been successfully used for several years to produce compositions containing about 70% (by weight) crystalline lycopene, which have been used in the food and beverage industry, especially in natural systems. Has been found to have commercial use as a health promoting food colorant.

U.S. Pat.No. 5,965,183

  However, there has been a need for many years for crystalline lycopene compositions with much better long-term stability and colorant properties.

  The present invention satisfies this need.

The present invention is primarily directed to compositions comprising lycopene crystals at a concentration greater than 70% (w / w) and methylene chloride insoluble material at a concentration less than 10%. It was unexpectedly found that the composition has very good properties as a colorant substance when compared to prior art compositions. In particular, the crystals of the composition of the present disclosure are easily ground to a size of less than 1 micron, preferably to the range of 50-500 nm. In addition, they are characterized by improved color parameters (eg Hunter, RS, December 1948, “Accuracy, Precision, and Stability of New Photo-electric Color-Difference Meter”, JOSA 38 (12): 1094, measured using the L ^* a ^* b ^* color parameter system). Preferably, the color parameters of the lycopene composition of the present disclosure and as set forth in the claims are as follows:
a value: ≧ 25;
b value: 11.25 to 14.5;
b / a = 0.45 to 0.55;
C value: 27.5-32.5;
h value: 24.2 to 27.0.

  In a preferred embodiment of the composition, at least one of the color parameters has a value as defined above. In another preferred embodiment, all of the parameters have the values defined above.

  Without being bound by theory, it is believed that both increased grinding ability and improved colorant properties are at least partially related to a reduction in insoluble matter concentration as well as high lycopene concentration.

  The present inventors have now found that (as compared to prior art compositions) lycopene compositions as defined above can be prepared with significantly reduced levels of methylene chloride insoluble material. This was achieved by using tomato pulp having a lycopene concentration much higher than that normally found in this type of tomato material. By way of example, such lycopene-rich tomato pulp can be produced by the methods disclosed and taught in co-owned international patent application publication WO2004 / 016104. This content is incorporated herein in its entirety. The method taught in this document can increase the lycopene concentration in the pulp thus obtained so that it is on the order of 5 to 15 times the lycopene concentration of the tomato from which the pulp was prepared. However, it should be noted that other methods can also be used to obtain a lycopene-rich tomato pulp preparation that can be used to produce the lycopene crystalline composition of the present invention.

  Accordingly, the present invention is also a method for preparing a lycopene composition as defined above, wherein the pulp is separated from crushed tomato, wherein the pulp has a lycopene concentration of at least 2000 ppm, Extracting with solvent to obtain oleoresin, separating lycopene crystals from the oleoresin, placing the lycopene crystals in a liquid medium that does not dissolve lycopene, and grinding the crystals to an average particle size of less than 1 micron. A preparation method comprising

  A specific method for preparing the composition is described in detail in Example 2 below.

  The inventors have now surprisingly found that when lycopene crystals are isolated from pulp prepared according to the teachings of WO2004 / 016104, the level of insoluble material present in the lycopene composition may be reduced by other methods (e.g., It was found to be significantly less than when compared to compositions prepared using tomato pulp material prepared by US 5,837,311). Since the tomato pulp produced by the method of WO2004 / 016104 has not been used as a raw material for preparing crystalline lycopene crystals, it has been obtained by the present inventors regarding a low concentration of insoluble substances in the composition of the present invention. The results obtained (see Example 5 below) were totally unexpected.

  The 70% (or greater) lycopene composition of the present invention can be prepared from the aforementioned high lycopene concentration pulp by any suitable method. However, in a preferred embodiment, the method described in commonly owned US 5,965,183 can be used. The contents of this publication are incorporated into this disclosure in their entirety.

  The present invention includes the aforementioned composition comprising at least 70% lycopene and less than 10% methylene chloride insoluble material. In a preferred embodiment, the composition comprises less than 9% of such insoluble materials. In another preferred embodiment, the composition comprises 7% or less insoluble material. In yet a further preferred embodiment, the composition comprises about 5% methylene chloride insoluble material.

  Generally, the lycopene crystals of the claimed composition are contained in a medium that does not substantially dissolve lycopene. In a preferred embodiment, the medium is glycerol. In another preferred embodiment, the medium can be selected from the group consisting of propylene glycol, water, lower alcohols such as ethanol, water miscible liquids and water soluble liquids.

  In the most preferred embodiment of the composition of the present invention, the size of the lycopene crystals is in the range of 50-500 nm.

  The invention also encompasses the use of the composition for coloring foods, beverages, nutritional supplements or cosmetics. The present invention further includes within its scope such colored foods and beverages and nutritional supplements or cosmetics. The actual color or hue achieved when using the compositions of the present invention for coloring or dyeing food or beverage products will depend on a variety of different factors. In general, however, the color achieved is in the red range of the spectrum.

Example 1
Production of lycopene crystals using prior art methods (comparative example)
One ton of ripe tomatoes containing 165 ppm lycopene (165 mg / kg) was washed and chopped.

  Tomato skin and seeds were separated from crushed tomatoes by sieving in two separate steps: an 8 mm sieve was used in the first step and a 2 mm sieve was used in the second step.

  After removing the skin and seeds, the resulting tomato juice was transferred to a container, which was evacuated using negative pressure for 30 minutes. The tomato juice was then heated to 82-86 ° C. with a heat exchanger and passed through a decanter to divide it into pulp (containing tomato fiber and lycopene) and sealam (containing soluble tomato solids). From 1 ton of tomato, 70 kg of wet pulp was obtained, the water content was 80%, and the lycopene concentration was 2000 ppm. The lycopene yield of this method was 95%.

  This wet pulp was used as a raw material for lycopene extraction. Ethyl acetate was used as the extraction solvent, in which case the ratio of ethyl acetate to tomato pulp was 2.9: 1 (w / w). Extraction was carried out at a temperature of 60 ° C. for 4 hours.

  About 1.25 kg of tomato oleoresin was obtained by this extraction method. The oleoresin content was 10% lycopene as measured by HPLC method. The yield of this method (by lycopene) was 92%.

  This tomato oleoresin was then used as a raw material for producing crystalline lycopene. 1.25 kg of tomato oleoresin was suspended in 5 kg of ethanol, heated to 60 ° C. and filtered through a 10 μm filter. After removing the solvent, 188 g of lycopene crystals were collected on the filter. The crystals so obtained contained 70% lycopene and 30% tomato oil. The yield of this process (by lycopene) was about 85%.

Example 2
Production of lycopene crystals according to the invention One ton of ripe tomatoes containing 165 ppm lycopene (165 mg / kg) was washed and chopped.

  Tomato skin and seeds were separated from crushed tomatoes through two types of sieves. For the first step, a 4 mm sieve was used, followed by a 0.8 mm sieve.

  After removing the skin and seeds, the tomato juice was placed in a container, which was evacuated using negative pressure for 30 minutes. The tomato juice was then heated to 82-86 ° C. with a heat exchanger and passed through a decanter to separate it into pulp (containing tomato fiber and lycopene) and sealam (containing soluble tomato solids). From 1 ton of tomato, 41 kg of wet pulp was obtained, the water content was 80%, and the lycopene concentration was 3800 ppm. The yield from this method with lycopene was 94%.

  This wet pulp was used as a raw material for lycopene extraction. Ethyl acetate was used as the extraction solvent and the ratio of ethyl acetate to tomato pulp was 2.0: 1 (w / w). Extraction was carried out at 60 ° C. for 4 hours. About 0.80 kg of tomato oleoresin was obtained by this extraction method. The oleoresin content was 15% lycopene as measured by HPLC method. The yield of this method (by lycopene) was 94%.

  Tomato oleoresin was then used as a raw material to produce crystalline lycopene. 0.90 kg of tomato oleoresin was suspended in 4 kg of ethanol, heated to 60 ° C. and filtered through a 10 μm filter. After removing the solvent, 155 g of lycopene crystals were collected on the filter. The crystals so obtained contained 85% lycopene and 15% tomato oil. The yield of this method (by lycopene) was about 85-87%.

Example 3
Determination of Insoluble Substance Concentration in the Composition of the Invention of different batches of the composition of the invention (prepared according to Example 2) as well as of the composition prepared by prior art methods (as described in Example 1) The concentration of methylene chloride insoluble material in the batch was determined by the following method based on the filtration of the sample solution and the insoluble content remaining on the filter.

Method:
Accurately weigh about 2.5 g sample into the flask and add methylene chloride (100 ml).
Sonicate the solution for 10 minutes.
• Cool the solution at 5 ° C for 30 minutes.
Filter the sample solution through a 0.8 μm PTFE membrane filter previously dried and weighed.
• Wash with 50 ml of methylene chloride at 5 ° C.
Dry the washed membrane filter at 85 ° C., cool in a desiccator containing dry silica gel, and record the weight of the dried filter.
Insoluble content (%) = ((weight of filter after use−weight of filter before use) / (weight of sample) × 100.

Example 4
Determination of lycopene concentration in tomato extract In addition to the methylene chloride insoluble substance assay described above, the lycopene concentration in tomato extract was measured spectrophotometrically. Briefly, 0.02-0.03 g of tomato extract was accurately weighed into a flask, followed by 10 ml of BHT solution (2.5 g of BHT in 0.5 liter of dichloromethane) and 50 ml of dichloromethane. The sample was dissolved by sonication in an ultrasonic bath. 5 ml of this solution was taken up in a 100 ml volumetric flask, made up with petroleum ether and then mixed well. The absorbance of this solution from 550 nm to 350 nm is scanned in a covered glass cuvette with an optical path of 1 cm using petroleum ether as a reference. Three specific extinction peaks are seen and the absorbance at about 472 nm (middle peak) is recorded (A ₄₇₂ ).

The lycopene concentration (by percentage) in the composition is determined using the following formula:
Lycopene% = (A ₄₇₂ × Dil × 100) / (gram weight of sample × 3,450).
Where A ₄₇₂ is the absorbance at ₄₇₂ nm; Dil is the dilution factor.

Example 5
Lycopene and Insoluble Substance Concentrations in Compositions of the Invention and Prior Art Compositions The percentage of insoluble material and percentage of lycopene was 42 batches of the composition of the invention (prepared according to Example 2) and about 70%. Each was measured (as described above) in 25 batches of a prior art composition (prepared according to Example 1) having a nominal lycopene concentration. The results obtained are summarized in the following table:

  As is apparent from the results presented in these tables, the claimed composition has an average lycopene concentration of 78.2% (w / w) ± 2.59 and 5.13% (w / w). w) It has an average insoluble substance concentration of ± 1.896. In contrast, the prior art composition has a low average lycopene concentration of 72.9% (w / w) ± 5.12 and a very high average insoluble concentration of 13.93% (w / w). ± 2.507.

Example 6
Formulation Analysis The following three formulation examples clearly show the unexpected relationship between the insoluble material concentration in the tomato-derived lycopene composition and the color characteristics of the composition. In these examples, the L ^* a ^* b ^* color characteristics of a 10 ppm aqueous solution of each formulation were determined using a Hunter Lab ColorQuest XE colorimeter and operating in transmission mode. Four individual batches of each formulation were subjected to this analysis. The important L ^* a ^* b ^* color parameters can be easily summarized as follows:
i) Parameter L is a measure of the brightness of the sample;
ii) Parameter a provides a measure of red saturation (if the parameter has a positive value) and green saturation (if the parameter has a negative value);
iii) Parameter b provides a measure of yellowness (positive value) and blueness (negative value).

  Parameter C (saturation or color intensity) and parameter h (hue angle) are calculated from the a and b values.

Formulations believed to have desirable color characteristics achieved the following L ^* a ^* b ^* target values:
a value: ≧ 25;
b value: 11.25 to 14.5;
b / a = 0.45 to 0.55;
C value: 27.5-32.5;
h value: 24.2 to 27.0.

Example 7
Colorant formulation containing lycopene crystals containing 5% insoluble material
10 kg crystalline lycopene (containing 5.1% insoluble material as measured by the method described above in Example 3)
20 kg sucrose ester 15 kg sunflower deoiled lecithin 300 g ascorbic acid 150 kg glycerol and water mixture
All ingredients were mixed using a high shear mixer until a homogeneous suspension was obtained. The size of the lycopene crystals was reduced from 50 to 100 μm to 50 to 400 nm by using a ball mill (the grinding chamber was 5 L). The grinding time was between 12 and 15 hours. As described above, L ^* a ^* b ^* color characteristics of a 10 ppm aqueous solution of the formulation are analyzed and L value = 42-47; a value = 25-28; b value = 11.5-14 I understood.

Stability:
The stability of the formulation was evaluated in beverages. Two beverage systems were used:
First beverage system: sugar syrup 11 ° Bx, pH = 3.0, ascorbic acid 200 ppm, lycopene 10 ppm;
Second beverage system: 5% fruit, 10 ° Bx and pH = 3.0-3.2, water-soluble flavor, ascorbic acid 200 ppm, lycopene content 5 ppm.

  The colored fruit compound was homogenized under a pressure of 150 Bar. Both beverages were pasteurized at 90-94 ° C. for 30 seconds. For the purpose of stability testing, the beverage was kept under fluorescent light at room temperature for 6 months. The control beverage was maintained at 4 ° C. in the refrigerator. Each month, the colored beverage was analyzed for the following parameters: (1) colorimetric values of L, a and b, (2) appearance of rings and (3) presence of precipitate.

The results obtained (the L ^* a ^* b ^* parameters are not significantly changed and there is no ring formation or precipitation) are shown for both beverages (colored with the lycopene composition of the present invention) for a test period of 6 months. It was completely stable during this period.

Example 8
Colorant formulation comprising lycopene crystals containing 7-9% insoluble material
10 kg crystalline lycopene (7.5% insoluble material as measured by the method described in Example 3 above).
20 kg sucrose ester 15 kg sunflower deoiled lecithin 300 g ascorbic acid 150 kg glycerol and water mixture
All ingredients were mixed using a high shear mixer until a homogeneous suspension was obtained. The size of lycopene crystals was reduced from 50 to 100 μm to 50 to 400 nm by using a ball mill (having a 5 L grinding chamber). The grinding time was about 20-22 hours. Color characteristics were analyzed as described above and found to be: L value = 42-47; a value = 25-28; b value 11.5-14. Although the milling time needed to be longer to achieve the same refinement achieved in Example 7 (with low insoluble matter concentration), the color parameters of these two formulations of the present invention Note that was the same.

The stability of the prepared formulation was evaluated in the following two beverage systems:
First beverage system-sugar syrup 11 ° Bx, pH = 3.0, ascorbic acid 200 ppm, lycopene 10 ppm;
Second beverage system: 5% fruit, 10 ° Bx and pH = 3.0-3.2, water-soluble flavor, ascorbic acid 200 ppm, lycopene content 5 ppm. The colored fruit compound was homogenized under a pressure of 150 Bar. Both beverages were pasteurized at 90-94 ° C. for 30 seconds. During the stability test period, the beverage was kept under fluorescent light at room temperature for 6 months. The control beverage was maintained at 4 ° C. in the refrigerator. Each month, the colored beverage was analyzed for the following parameters:
(1) Colorimetric values of L, a and b, (2) Appearance of rings and (3) Presence of precipitates.

The results obtained (the L ^* a ^* b ^* parameters are not significantly changed and there is no ring formation or precipitation) are shown for both beverages (colored with the lycopene composition of the present invention) for a test period of 6 months. It was completely stable during this period.

Example 9
Colorant formulation containing lycopene crystals containing 15% insoluble material (comparative example)
material:
10 kg crystalline lycopene (15.2% insoluble material as measured by the method described in Example 3 above)
20 kg sucrose ester 15 kg sunflower deoiled lecithin 300 g ascorbic acid 150 kg glycerol and water mixture All ingredients were mixed to a homogeneous suspension using a high shear mixer. The size of lycopene crystals was reduced from 50 to 100 μm to 50 to 400 nm by using a ball mill (having a 5 L grinding chamber). The grinding time was about 27 to 48 hours.

  The color characteristics of the lycopene composition were analyzed as described above and found to be: L value = 40-47; a value = 20-23; b value 14-19. Note that although longer milling times were used, it was not possible to obtain the desired color intensity and hue with this composition having a high concentration of insoluble material.

The stability of the prepared formulation was evaluated in the following two beverage systems:
First beverage system-sugar syrup 11 ° Bx, pH = 3.0, ascorbic acid 200 ppm, lycopene 10 ppm;
Second beverage system: 5% fruit, 10 ° Bx and pH = 3.0-3.2, water-soluble flavor, ascorbic acid 200 ppm, lycopene content 5 ppm. The colored fruit compound was homogenized under a pressure of 150 Bar. Both beverages were pasteurized at 90-94 ° C. for 30 seconds. For the purpose of stability testing, the beverage was kept under fluorescent light at room temperature for 6 months. The control beverage was maintained at 4 ° C. in the refrigerator. Each month, the colored beverage was analyzed for the following parameters: (1) Colorimetric values of L, a and b, (2) Appearance of rings and (3) Presence of precipitates.

  The results obtained (ring formation) indicate that after only 1 to 2 months the stability has been lost in the first beverage system. Furthermore, the color intensity is greater when this formulation is used (in both beverage systems) compared to the formulation containing less than 10% insoluble material (Formulation Example 7 and Formulation Example 8 above). ) It was quite low.

  Color value results obtained with two different formulations of the present invention (5% and 7-9% insoluble material; Formulation Example 7 and Formulation Example 8) and prior art formulations (15% insolubility) Substances) are summarized in the following table:

  It is clear from these results that the desired a value (≧ 25; as explained above) was obtained only with two formulations containing less than 10% insoluble material. When testing a prior art formulation containing 15% insoluble material, the a value was less than the target value. Similarly, only two test formulations with less than 10% insoluble material were found to have a / b values within the target range (0.45-0.55). Finally, the color intensity values (C) and hue values (h) for the two formulations of the present invention were both within the desired range, but the prior art compositions deviated significantly from the target values. Had a value.

  We conclude that lycopene compositions having less than 10% insoluble material have unexpectedly superior color characteristics when compared to compositions having more than 10% insoluble components. In addition, for compositions having less than 10% insoluble material, the grinding time required to achieve the desired lycopene crystal size and color properties is reduced as the concentration of the insoluble material decreases. I understand.

Claims (13)

  A tomato-derived composition comprising lycopene crystals at a concentration of at least 70% (w / w) and methylene chloride insoluble material at a concentration of 10% (w / w) or less, wherein the size of the lycopene crystals is less than 1 micron ,Composition.   The composition of claim 1, wherein the concentration of methylene chloride insoluble material is less than 9% (w / w).   The composition of claim 2, wherein the concentration of methylene chloride insoluble material is less than 7% (w / w).   4. The composition of claim 3, wherein the concentration of methylene chloride insoluble material is about 5% (w / w).   The composition of claim 1, wherein the size of the lycopene crystals is in the range of 50 nm to 500 nm.   The composition of claim 1, wherein the color parameter “a” is greater than 25.   The composition of claim 1, wherein the color parameter “b” is in the range of 11.25 to 14.5.   The composition of claim 1, wherein the ratio of the color parameter "b" to the color parameter "a" is in the range of 0.45 to 0.55.   The composition of claim 1, wherein the color parameter "C" is in the range of 27.5 to 32.5.   The composition of claim 1, wherein the color parameter “h” ranges from 24.2 to 27.0.   Use of the composition according to claim 1 as a colorant for foods, beverages, nutritional supplements or cosmetics.   A method for preparing a composition according to claim 1, wherein the pulp is separated from crushed tomatoes, wherein the pulp has a lycopene concentration of at least 2000 ppm, the pulp is extracted with a solvent and oleole. Obtaining gin, separating lycopene crystals from said oleoresin, placing said lycopene crystals in a liquid medium that does not dissolve lycopene, and grinding said crystals to an average particle size of less than 1 micron. . The composition obtained by the method is
A value exceeding 25,
b value: 11.25 to 14.5;
b / a = 0.45 to 0.55;
C value: 27.5 to 32.5;
h value: 24.2 to 27.0
13. The method of claim 12, having one or more color parameters selected from the group consisting of: